Future work will be focused on the new highly organized artificial
structures based on the oligo(phenanthroline dicarboxamide)
helical foldamers, and their potential applications in asymmetric
catalysis and materials science.
121.6, 120.8, 120.4, 120.3, 120.2, 120.1, 102.2, 101.6, 101.4, 101.3,
101.2, 101.1, 101.0, 100.89, 100.85, 100.8, 100.7, 100.6, 100.5, 75.5,
75.4, 75.1, 75.0, 74.8, 74.7, 28.6, 28.5, 28.3, 28.2, 28.1, 19.8, 19.5,
19.4, 19.3, 19.0, 18.9. MALDI TOF MS: m/z 3116 [M + H]+.
Anal. Calcd. for C182H176N24O26·2H2O: C, 69.36; H, 5.76; N, 10.67.
Found: C, 69.40; H, 5.76; N, 10.59%.
Experimental
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1
Compound 4. Yield: 98%. Mp >300 C. H NMR (CDCl3,
600 MHz): 14.60 (s, 2H, NH), 11.37 (bs, 2H, NH), 9.17 (s, 2H, J =
8.3 Hz), 8.42–8.38 (m, 4H), 8.11 (s, 2H), 7.73–7.69 (m, 6H), 7.30
(t, 2H, J = 7.9 Hz), 7.02 (bs, 4H), 6.81 bs, 2H), 4.32–4.22 (m, 8H,
-OCH2CH(CH3)2), 2.43–2.36 (m, 4H, -OCH2CH(CH3)2), 1.24–
1.22 (m, -OCH2CH(CH3)2, 24H). 13C NMR (CDCl3, 150 MHz):
187.7, 164.6, 163.5, 151.3, 140.4, 137.5, 135.5, 134.6, 128.3, 126.2,
124.6, 123.8, 123.2, 123.0, 121.5, 121.0, 120.7, 118.1, 102.2, 96.1,
75.6, 28.3, 19.3. MALDI TOF MS: m/z 1200 [M + Na]+. Anal.
Calcd. for C70H64N8O10·H2O: C, 70.34; H, 5.57; N, 9.37. Found:
C, 70.44; H, 5.59; N, 9.48%.
General method for the synthesis of oligomers 1–6
To a solution of the diaminoanthraquinone 10 or 11 (1.19 g,
0.5 mmol) in CH2Cl2 (50 mL) was added the corresponding acid
(1.5 mmol), 1-hydroxylbenzotriazole (HOBt) (230 mg, 1.5 mmol),
and DCC (309 mg, 1.5 mmol). The reaction mixture was stirred at
room temperature, and then refluxed for about 2 weeks. The pre-
cipitates were removed by filtration through Celite. The solution
was concentrated, and the residue was washed with MeOH. The
solid was purified by silica-gel column chromatography (ethyl
acetate–dichloromethane–petrol ether 1 : 2 : 3) to give the product
as an orange solid.
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1
Compound 5. Yield: 96%. Mp >300 C. H NMR (CDCl3,
600 MHz): 13.38 (bs, 2H, NH), 11.60 (s, 2H, NH), 11.39 (bs,
2H, NH), 11.00 (bs, 2H, NH), 9.02 (bs, 2H), 8.33 (d, 2H, J =
9.0 Hz), 8.24 (bs, 4H), 8.18 (d, J = 9.0 Hz, 2H), 7.79–7.50 (m,
20H), 7.20 (bs, 4H), 7.31 (bs, 2H), 7.05 (bs, 4H), 6.96 (t, 2H,
J = 7.3 Hz), 4.24–4.36 (m, 16H, -OCH2CH(CH3)2), 2.40–2.16 (m,
8H, -OCH2CH(CH3)2), 1.23–1.09 (m, -OCH2CH(CH3)2, 48H).
13C NMR (CDCl3, 150 MHz): 164.0, 163.6, 163.3, 163.2, 162.8,
162.7, 151.4, 151.3, 150.4, 145.43, 145.35, 145.25, 145.18, 145.13,
145.09, 140.2, 138.0, 134.6, 130.2, 128.9, 126.12, 126.09, 125.2,
124.3, 124.2, 123.4, 122.9, 122.52, 122.47, 122.42, 122.40, 121.05,
121.02, 120.99, 120.44, 120.40, 120.33, 120.31, 120.2, 118.3, 102.3,
101.7, 101.63, 101.60, 75.6, 75.4, 74.8, 28.5, 28.42, 28.39, 19.49,
19.45. MALDI TOF MS: m/z 2169 [M + Na]+. Anal. Calcd. for
C126H120N16O18: C, 70.51; H, 5.64; N, 10.44. Found: C, 70.42; H,
5.72; N, 10.38%.
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1
Compound 1. Yield: 91%. Mp >300 C. H NMR (CDCl3,
600 MHz): 14.21 (s, 2H, NH), 10.50 (bs, 2H, NH), 9.60 (s, 2H),
8.41–8.37 (m, 4H), 8.23 (bs, 2H), 8.12 (s, 2H), 7.66–7.60 (m, 6H),
6.94–6.93 (m, 4H), 6.84 (bs, 4H), 6.62 (bs, 2H), 4.27–4.21 (m, 8H,
-OCH2CH(CH3)2), 2.42–2.35 (m, 4H, -CH2CH(CH3)2), 1.22–1.21
(m, -CH2CH(CH3)2, 24H). 13C NMR (CDCl3, 150 MHz): 188.1,
165.0, 163.5, 151.7, 151.4, 145.7, 138.1, 137.7, 133.5, 132.4, 129.7,
128.4, 127.0, 124.4, 123.2, 123.0, 120.9, 120.7, 119.8, 102.3, 75.7,
28.4, 19.5. MALDI TOF MS: m/z 1178 [M + H]+. Anal. Calcd.
for C70H64N8O10: C, 71.41; H, 5.48; N, 9.52. Found: C, 71.22; H,
5.57; N, 9.36%.
Compound 2. Yield: 93%. Mp 296–298 ◦C. 1H NMR (CDCl3,
600 MHz): 14.09 (s, 2H, NH), 11.61 (s, 2H, NH), 11.36 (s, 2H,
NH), 11.61 (bs, 2H, NH), 9.36 (s, 2H), 8.38 (d, 2H, J = 9.1 Hz),
8.26–8.24 (m, 4H), 8.15 (d, J = 9.1 Hz, 2H), 8.06 (bs, 2H), 7.77–
7.52 (m, 16H), 7.31 (bs, 2H), 7.20 (bs, 4H), 7.06 (t, 2H, J = 6.7 Hz),
6.98–6.91 (m, 4H), 4.15–4.02 (m, 12H, -OCH2CH(CH3)2), 3.54
(bs, 4H, -OCH2CH(CH3)2), 2.40–2.17 (m, 8H, -OCH2CH(CH3)2),
1.23–1.11 (m, -OCH2CH(CH3)2, 48H).13C NMR (CDCl3,
150 MHz): 188.1, 164.1, 163.5, 163.3, 163.2, 162.7, 162.6, 161.9,
151.4, 151.3, 150.6, 150.2, 145.4, 145.3, 145.2, 145.0, 137.9, 137.5,
134.3, 132.2, 130.3, 129.0, 128.3, 126.5, 125.8, 124.1, 123.0, 122.8,
122.4, 121.1, 120.2, 119.8, 102.3, 101.6, 75.6, 75.5, 75.4, 74.7,
39.1, 38.9, 34.3, 32.9, 32.0, 29.8, 29.6, 29.4, 29.2, 28.5, 28.4,
28.1, 23.1, 22.85, 22.82, 20.3, 19.5, 19.4, 19.3, 14.6, 14.33, 14.28,
11.6. MALDI TOF MS: m/z 2169 [M + Na]+. Anal. Calcd. for
C126H120N16O18·2H2O: C, 69.34; H, 5.73; N, 10.27. Found: C, 69.56;
H, 5.93; N, 9.85%.
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1
Compound 6. Yield: 89%. Mp >300 C. H NMR (CDCl3,
600 MHz): 13.06 (bs, 2H, NH), 11.04–9.76 (m, 10H, NH), 8.30–
6.49 (m, 56H), 4.05–3.61 (m, 24H, -OCH2CH(CH3)2), 2.35–2.06
(m, 12H, -OCH2CH(CH3)2), 1.25–1.00 (m, -OCH2CH(CH3)2,
72H). 13C NMR (CDCl3, 150 MHz): 164.1, 164.0, 163.8, 163.6,
163.5, 163.4, 163.42, 163.35, 163.2, 163.0, 162.7, 162.5, 162.4,
162.3, 162.2, 162.04, 161.98, 161.91, 161.87, 161.7, 161.43, 161.36,
161.3, 151.7, 151.5, 151.4, 151.3, 150.9, 150.8, 150.7, 150.6, 150.5,
150.43, 150.39, 150.3, 150.2, 150.2, 150.1, 150.0, 149.9, 149.8,
149.6, 149.5, 149.44, 149.38, 145.36, 145.3, 145.0, 144.8, 144.4,
139.4, 139.35, 139.30, 138.1, 134.0, 133.8, 133.6, 130.7, 128.8,
125.6, 124.0, 123.2, 122.8, 122.5, 122.3, 122.1, 121.3, 120.8, 120.4,
120.3, 120.1, 119.8, 119.7, 119.6, 117.85, 117.79, 102.1, 101.82,
101.76, 101.7, 101.6, 101.4, 101.32, 101.26, 101.1, 101.0, 100.9,
100.8, 100.7, 100.6, 100.5, 100.4, 100.3, 100.24, 100.20, 100.1,
75.5, 75.0, 29.9, 28.4, 28.3, 28.1, 27.9, 19.8, 19.5, 19.4, 19.3,
18.8. MALDI TOF MS: m/z 3138 [M + Na]+. Anal. Calcd. For
C182H176N24O26·H2O: C, 69.76; H, 5.73; N, 10.73. Found: C, 69.63;
H, 5.84; N, 10.62%.
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1
Compound 3. Yield: 84%. Mp >300 C. H NMR (CDCl3,
600 MHz): 13.56 (bs, 2H, NH), 11.14–10.11 (m, 10H, NH),
8.83–6.19 (m, 56H), 4.03–3.61 (m, 24H, -OCH2CH(CH3)2), 2.33–
1.96 (m, 12H, -OCH2CH(CH3)2), 1.25–0.87 (m, -OCH2CH(CH3)2,
72H). 13C NMR (CDCl3, 150 MHz): 163.4, 163.3, 163.0, 162.9,
162.8, 162.7, 162.5, 162.3, 162.2, 162.10, 162.06, 162.0, 161.9,
161.8, 161.70, 161.66, 161.6, 161.5, 160.7, 151.1, 151.0, 150.9,
150.3, 150.2, 150.1, 150.0, 149.94, 149.89, 149.82, 149.7, 149.6,
145.3, 145.2, 145.1, 145.10, 145.05, 144.8, 144.5, 138.0, 137.1,
131.4, 130.3, 128.9, 128.6, 126.2, 125.8, 125.3, 125.2, 124.5, 124.4,
124.3, 124.0, 123.3, 123.1, 122.8, 122.3, 122.2, 122.10, 122.05,
Acknowledgements
We thank the National Natural Science Foundation of China
(20625206), CMS-CX200826, and National Basic Research
2538 | Org. Biomol. Chem., 2009, 7, 2534–2539
This journal is
The Royal Society of Chemistry 2009
©